Flame-retardant heat-resistant resin composition and adhesive film comprising the same

ABSTRACT

The present invention provides a non-flammable heat-resistant resin composition that is provided with (A) modified polyamideimide resin, (B) thermosetting resin and (C) organic phosphor-based compound, and a cured film, obtained from the non-flammable heat-resistant resin composition, exerts a storage elastic modulus of 700 MPa or less, a coefficient of thermal expansion of 5×10 −3 /K or less and an internal stress of 20 MPa or less, in a temperature range of 25 to 250° C., and the present invention also relates to an adhesive film using the resin composition.

FIELD OF THE INVENTION

The present invention relates to a non-flammable heat-resistant resincomposition that has superior thermal-stress reducing effects, and iseffectively used for adhesives for various printed circuit boards,adhesive films and the like, and also concerns an adhesive film usingsuch a resin composition.

BACKGROUND OF THE INVENTION

In recent years, along with the developments of various small-size,lightweight electronic apparatuses, the packaging density of electronicparts becomes higher, and there have been various demands forcharacteristics required for various electronic parts and materials tobe used in these apparatuses. In particular, with respect to printedcircuit boards, the circuit occupied area becomes smaller, and comes tohave a higher density, and there have been increasing demands formulti-layer circuit boards (built-up circuit boards), flexible wiringboards (FPC) and the like. With respect to these circuit boards, variousadhesives and adhesive films are used in manufacturing processesthereof, and with respect to resins to be used for the adhesives, epoxyresins, acrylic resins and the like are mainly used. However, none ofthese resins sufficiently satisfy characteristics such as heatresistance and electrical insulating property.

Here, adhesives made from polyimide resins and polyamideimide resinshave been known as adhesives having superior heat resistance andelectrical insulating property; however, these adhesives have a problemin that a thermal stress is generated between a coated member and theadhesive due to thermal history during circuit board manufacturingprocesses to cause warping in the resulting wiring circuit board.

Conventionally, with respect to the non-flammable agent for materialsfor various printed circuit boards, halogen-based compounds andantimony-based compounds, such as brome-based compounds, having superiornon-flammable effects have been generally used. However, with respect tothe halogen-based compounds, recent researches have implied thepossibility of generating gases containing dioxin and the like highlytoxic to the human body, upon burning, and the application thereof hasbeen limited centered on European countries. With respect to substitutesfor such non-flammable agents, well-known specific examples includeinorganic fillers, such as aluminum hydroxide and magnesium hydroxide,and non-flammable agents such as phosphor-based compounds.

However, with respect to these compounds, in order to obtain asufficient non-flammable property, a great amount thereof needs to beadded to a target resin, with the result that the inherentcharacteristics of the resin tend to deteriorate greatly. Morespecifically, it has been known that, for example, in an FPC-useadhesive among various circuit-board-use adhesives, due to solublesodium mixed therein upon production, aluminum hydroxide tends to causea hydrolytic reaction on the surface of a polyimide film that is acoated member, when subjected to a long-time high-temperature,high-humidity process, to weaken the surface of the polyimide film tocause degradation in the peeling strength. Moreover, it has beengenerally known that magnesium hydroxide causes degradation in acidresistance. Furthermore, phosphates, which have been well knownmaterials among phosphor-based compounds, function as a plasticizer tocause degradation in the heat resistance and the like; therefore, it isnecessary to limit the kinds and added amounts thereof.

SUMMARY OF THE INVENTION

An objective of the present invention is to provide a non-flammableheat-resistant resin composition which exerts superiorthermal-stress-reducing effects, and is effectively used for adhesivesfor various printed circuit boards and adhesive films. Moreover, anotherobjective thereof is to provide a non-flammable heat-resistant resincomposition which has a superior halogen-free non-flammable propertyderived from a phosphor-based compound serving as a non-flammableassistant agent, and a superior adhesive property derived from amodified polyamideimide resin, and is effectively used for variousprinted-circuit-use adhesives and adhesive films.

Still another objective of the present invention is to provide anadhesive film which has superior halogen-free heat resistant propertyand non-flammable property, and also has a superior adhesive propertyderived from a modified polyamideimide resin, and is effectively usedfor various printed circuit boards.

In other words, the present invention relates to a non-flammableheat-resistant resin composition that contains (A) modifiedpolyamideimide resin, (B) thermosetting resin and (C) organicphosphor-based compound, and the cured film, obtained from thecomposition, exerts a storage elastic modulus of 700 MPa or less, acoefficient of thermal expansion of 5×10⁻³/K or less and an internalstress of 20 MPa or less, in a temperature range of 25 to 250° C.

Moreover, the present invention also relates to the above-mentionednon-flammable heat-resistant resin composition in which: the modifiedpolyamideimide resin of (A) component is synthesized in the presence ofa non-protic polar solvent, and resin varnish containing this solvent isdried at 120 to 140° C. for 5 to 15 minutes so that the content of thenon-protic polar solvent becomes 1% or less.

Furthermore, the present invention relates to the above-mentionednon-flammable heat-resistant resin composition which contains 10 to 100parts by weight of the thermosetting resin of (B) component and 2 to 20parts by weight of the organic phosphor-based compound of (C) component,with respect to 100 parts by weight of the modified polyamideimide resinof (A) component.

In the present invention, the modified polyamideimide resin of (A)component is a modified polyamideimide resin that is obtained byallowing a mixture containing diimide dicarboxylic acid, represented bythe following formula 1, formula 2 and formula 3 obtained through areaction between a mixture of diamine having three or more aromaticrings, polyoxypropylene diamine and siloxane diamine, and trimelliticanhydride;

[in the formula, R¹ represents:

(where X represents

[in the formula, R² represents:

(where n represents an integer of 1 to 70).]

[in the formula, R³ represents:

(where R⁴ and R⁵ independently represent divalent organic groups, eachof R⁶ to R⁹ independently represents an alkyl group having 1 to 20carbon atoms or an aryl group having 6 to 18 carbon atoms, and mrepresents an integer of 1 to 50)]and aromatic dicarboxylic acid represented by the following formula 4 tocoexist;HOOC—R¹⁰—COOH  (Formula 4)[in the formula, R¹⁰ represents:

and by also allowing aromatic diisocyanate represented by the followingformula 5 to react with the mixture.NCO—R¹¹—NCO  (Formula 5)[in the formula, R¹¹ represents:

Moreover, the present invention relates to the above-mentionednon-flammable heat-resistant resin composition in which the modifiedpolyamideimide resin component (A) is synthesized in the presence of abasic catalyst, and the basic catalyst is trialkyl amine represented bythe following formula 6.

(in the formula, each of R¹² to R¹⁴ represents an alkyl group having 1to 8 carbon atoms.)

Further, the present invention relates to the above-mentionednon-flammable heat-resistant resin composition in which the amineequivalent weight of polyoxypropylene diamine is set in a range from 100to 2,000 g/mol.

Moreover, the present invention relates to the above-mentionednon-flammable heat-resistant resin composition in which the amineequivalent weight of siloxane diamine is set in a range from 400 to2,500 g/mol.

Furthermore, the present invention relates to the above-mentionednon-flammable heat-resistant resin composition in which thethermosetting resin component (B) is made from an epoxy resin and acuring accelerator thereof or a curing agent thereof.

Here, the present invention also relates to the above-mentionednon-flammable heat-resistant resin composition in which the epoxy resinis a phosphor-containing epoxy resin.

Further, the present invention relates to the above-mentionednon-flammable heat-resistant resin composition in which the organicphosphor-based compound (C) is a phosphate-based compound represented bythe following formula 7,

(in the formula, W represents a single bond, or a bonding group, such asan alkylene group having 1 to 5 carbon atoms, —S—, —SO₂—, —O—, or —N═N—,and n₁ is an integer of 10 to 50) or a phosphate-based compoundrepresented by the following formula formula 8.

(in the formula, n₂ is an integer of 10 to 50)

Moreover, the present invention relates to an adhesive film having atleast the above-mentioned non-flammable heat-resistant resin compositionand a supporting member for supporting the resin composition, and thesupporting member is preferably made of a polyimide film.

This application claims benefit of priority to Japanese patentapplications No. 2001-269141 (filing date: Sep. 5, 2001) and No.2002-137309 (filing date: May 13, 2002), previously applied by the sameapplicant as the present application, the specifications of which areincorporated by reference herein.

DETAILED DESCRIPTION OF THE INVENTION

The non-flammable heat-resistant resin composition of the presentinvention contains (A) modified polyamideimide resin, (B) thermosettingresin and (C) organic phosphor-based compound.

Moreover, a cured film, obtained from the above-mentioned non-flammableheat-resistant resin composition, exerts a storage elastic modulus of700 MPa or less, preferably, from 50 to 600 MPa, a coefficient ofthermal expansion of 5×10⁻³/K or less, preferably, 4×10⁻³/K to0.2×10⁻³/K, and an internal stress of 20 MPa or less, preferably, 1 to18 MPa, in a temperature range of 25 to 250° C. Here, the glasstransition temperature (Tg) thereof is preferably set in a range from 25to 250° C., more preferably, from 50 to 230° C., most preferably, from100 to 200° C.

In the case when the storage elastic modulus exceeds 700 MPa, thecoefficient of thermal expansion exceeds 5×10⁻³/K and the internalstress exceeds 20 MPa, it becomes difficult to reduce warping byalleviating the stress. Here, in the present invention, the storageelastic modulus is measured by a dynamic viscoelasticity measuringdevice (DMA). The coefficient of thermal expansion is measured by athermal mechanical analyzer (TMA). The internal stress (a) is found fromthe following equation based upon the coefficient of thermal expansion(a), the storage elastic modulus (E) and the glass transitiontemperature (Tg).σ=α₁E₁(Tg−Tg₁)+α₂E₂(Tg₂−Tg)

Here, α₁ represents a coefficient of thermal expansion at temperatureslower than Tg, and α₂ represents a coefficient of thermal expansion attemperatures higher than Tg. Moreover, E₁ represents a storage elasticmodulus at temperatures lower than Tg, and E₂ represents a storageelastic modulus at temperatures higher than Tg. Further, Tg₁ is apredetermined set temperature lower than Tg, and Tg₂ is a predeterminedset temperature higher than Tg.

Additionally, these physical properties can be measured by using a curedfilm obtained by the non-flammable heat-resistant resin composition ofthe present invention. With respect to the forming conditions of thecured film, although not particularly limited, for example, the curedfilm, obtained through a curing process at 180° C. for 2 hours, may beused for the measurements.

The modified polyamideimide resin of (A) component is a polyamideimideresin that is preferably obtained by allowing: a mixture containingdiimide dicarboxylic acid represented by the above-mentioned formula 1,formula 2 and formula 3 obtained through a reaction between a mixture ofdiamine having three or more aromatic rings, polyoxypropylene diamineand siloxane diamine, and trimellitic anhydride; aromatic dicarboxylicacid represented by the following formula 4; and aromatic diisocyanaterepresented by the following formula 5 to react with one another byusing a basic catalyst represented by the above-mentioned formula 6.

In the above-mentioned formula 3, with respect to the alkyl group having1 to 20 carbon atoms, examples thereof include: a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group,an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, an undecyl group, a dodecylgroup, a tridecyl group, a tetradecyl group, a pentadecyl group, ahexadecyl group, a heptadecyl group, an octadecyl group, a nonadecylgroup and icocyl group and structural isomers of these.

In the above-mentioned formula 3, with respect to the aryl group having6 to 18 carbon atoms, examples thereof include: a phenyl group, anaphthyl group, an anthoryl group and a phenantholyl group, and thesemay be substituted by a halogen atom, an amino group, a nitro group, acyano group, a mercapto group, an allyl group, an alkyl group having 1to 20 carbon atoms or the like.

With respect to the diamine having three or more aromatic rings,examples thereof include:

-   2,2-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter, sometimes    referred to simply as BAPP),-   bis[4-(3-aminophenoxy)phenyl]sulfone,-   2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,-   bis[4-(4-aminophenoxy)phenyl]methane,-   4,4′-bis(4-aminophenoxy)biphenyl,-   bis[4-(4-aminophenoxy)phenyl]ether,-   bis[4-(4-aminophenoxy)phenyl] ketone,-   1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy) benzene, and    from the viewpoints of balance of characteristics and costs of the    modified polyamideimide resin,-   2,2-bis[4-(4-aminophenoxy)phenyl]propane is more preferably used.    These may be used alone or two or more kinds of these may be used in    combination.

With respect to polyoxypropylene diamine to be used in the presentinvention, known compounds may be used, and for example, compoundsrepresented by the following formula 9 are preferably used:

(where n is an integer of 1 to 70).

Commercially available products thereof include: Jeffermine D-230 (amineequivalent 115 g/mol), Jeffermine D-400 (amine equivalent 200 g/mol),Jeffermine D-2000 (amine equivalent 1,000 g/mol) and Jeffermine D-4000(amine equivalent 2,000 g/mol) (trade names of Sun Technochemical Co.,Ltd.). These may be used alone or two or more of these may be used incombination.

Here, in order to allow the modified polyamideimide resin of (A)component to reduce the thermal stress that causes warping and improvethe adhesiveness, the amine equivalent weight of polyoxypropylenediamine is preferably set in a range from 100 to 2,000 g/mol,preferably, from 200 to 2,000 g/mol, more preferably, from 1,000 to2,000 g/mol. Examples thereof include Jeffermine D-2000 (amineequivalent weight: 1,000 g/mol), Jeffermine D-4000 (amine equivalentweight: 2,000 g/mol) (trade names: made by Sun Technochemical Co.,Ltd.), and the like. These may be used alone or two kinds or more ofthese may be used in combination. Here, in the present invention, theamine equivalent weight refers to the number of grams of a resin thatcontains 1 mol of amino groups.

With respect to siloxane diamine to be used in the present invention,those of conventionally known compounds may be used, and, for example,the compound represented by the following formula 10 is preferably used:

(in the formula, R¹⁵ and R¹⁶ independently represent divalent organicgroups, R¹⁷ to R²⁰ are independently defined in the same manner as R⁶ toR⁹ in the above-mentioned formula 3, and n represents an integer of 1 to50.)

In the above-mentioned formula (formula 10), with respect to thedivalent organic group, examples thereof include: alkylene groups suchas a methylene group, an ethylene group and a propylene group, andarylene groups such as a phenylene group, a tolylene group and axylylene group, and the arylene group may have a substituent such as analkyl group.

With respect to siloxane diamine of this type, those represented by thefollowing formulas are listed:

[in the formulas, m represents an integer of 1 to 50.]

Examples of those commercially available include amino-modified siliconeoils, which are siloxane-based diamines having amine groups on two ends:X-22-161AS (amine equivalent weight: 450 g/mol), X-22-161-A (amineequivalent weight: 840 g/mol) and X-22-161-B (amine equivalent weight:1540 g/mol) (trade names, made by Shin-Etsu Chemical Co., Ltd.) and thelike, and BY16-853 (amine equivalent weight: 650 g/mol), BY16-853B(amine equivalent weight: 2200 g/mol) (trade names, made by Dow CorningToray Silicone Co., Ltd.) and the like. These may be used alone, or twoor more kinds of these may be used in combination.

Here, in order to impart a non-flammable property to the modifiedpolyamideimide resin of (A) component and to improve the adhesiveness,the amine equivalent weight of siloxane diamine is preferably set in arange from 400 to 2,500 g/mol, more preferably, from 800 to 2,500 g/mol,most preferably, from 800 to 1,600 g/mol. Examples of these includeX-22-161A (amine equivalent weight: 840 g/mol), X-22-161B (amineequivalent weight: 1540 g/mol) (trade names, made by Shin-Etsu ChemicalCo., Ltd.) and the like. These may be used alone, or two or more kindsof these may be used in combination.

With respect to aromatic dicarboxylic acid represented by theabove-mentioned formula 4, examples thereof include: terephthalic acid,isophthalic acid, 1,4-naphthalene dicarboxylic acid and 2,6-naphthalenedicarboxylic acid, from the viewpoints of improving the aligningproperty of polymer, the film-forming property and the heat resistancethereof, terephthalic acid is preferably used. These may be used alone,or two or more kinds of these may be used in combination. Moreover,aliphatic dicarboxylic acid, such as adipic acid, sebacic acid, decanoicdiacid and dodecanoic diacid, may be added to the above-mentionedaromatic dicarboxylic acid at a rate of 5 to 10 mol %.

With respect to the aromatic diisocyanate represented by theabove-mentioned formula 5, examples thereof include:4,4′-diphenylmethane diisocyanate (hereinafter, sometimes referred tosimply as MDI), 2,4-tolylenediisocyanate (hereinafter, sometimesreferred to simply as TDI), 2,6-tolylenediisocyanate,naphthalene-1,5-diisocyanate, 2,4-tolylene dimer, and the like, and fromthe viewpoints of imparting flexibility and of preventing crystallineproperty, 4,4′-diphenylmethane diisocyanate is preferably used. Thesemay be used alone, or two or more kinds of these may be used incombination.

Moreover, from the viewpoint of heat resistance, aliphatic diisocyanate,such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylenediisocyanate and isophoronediisocyanate, may be used at a rate of 5 to10 mol % in combination with the above-mentioned aromatic diisocyanate.

With respect to the basic catalyst represented by the above-mentionedformula 6, examples thereof include: trimethyl amine, triethyl amine,tripropyl amine, tri(2-ethylhexyl)amine and trioctyl amine, and triethylamine, which accelerates the polymerization reaction, and is easilyremoved, is preferably used.

The modified polyamideimide resin of (A) component to be used in thepresent invention is prepared by, for example, the following processes:diamine (1′) having three or more aromatic rings, polyoxypropylenediamine (2′) and siloxane diamine (3′), as well as trimellitic anhydride(hereinafter, referred to simply as TMA), are allowed to react with oneanother at 160° C. for two hours in the presence of a non-protic polarsolvent and aromatic hydrocarbon (at a weight ratio of 0.1 to 0.5 withrespect to the non-protic polar solvent) capable of azeotropicdistillation together with water; thus, a mixture containing aromaticdiimide dicarboxylic acid (1) represented by the above-mentioned formulaformula 1, polyoxypropylene diimide dicarboxylic acid (2) represented bythe above-mentioned formula 2 and siloxane diimide dicarboxylic acid (3)represented by the above-mentioned formula 3 is prepared, and thismixture is allowed to react with aromatic dicarboxylic acid (4)represented by the above-mentioned formula 4 and aromatic diisocyanate(5) represented by the above-mentioned formula 5 at 190° C. for twohours.

Moreover, after the mixture containing diimide carboxylic acidsrepresented by the above-mentioned formula formula 1, formula 2 andformula 3 has been prepared, the resulting solution is heated to 160 to190° C. so that the aromatic hydrocarbon capable of azeotropicdistillation together with water is removed therefrom, and aromaticdicarboxylic acid is added thereto to allow this to react with aromaticdiisocyanate; thus, the modified polyamideimide resin of (A) componentis also obtained. Here, the modified polyamideimide resin is preferablyprepared as varnish containing a non-protic polar solvent.

With respect to a ratio of blending of the mixture of diamine (1′)having three or more aromatic rings, polyoxypropylene diamine (2′) andsiloxane diamine (3′), the ratio is preferably set to (1′)/(2′)/(3′)=(0to 70.0)/(10.0 to 70.0)/(10.0 to 50.0)(in which the unit of therespective values is mole % and the total of (1′)(2′) and (3′) is 100mole %), and a resin obtained by using a mixture having a ratio out ofthis range tends to cause warping, or degradation in the non-flammableproperty, or disappearance of the micro phase separation structure, or areduction in the molecular weight. The range of the ratio is morepreferably set to (0 to 65.0)/(20.0 to 60.0)/(10.0 to 40.0)(mole %).

Moreover, the amounts of materials to be used for allowing theabove-mentioned mixture to react with trimellitic anhydride (TMA) toobtain a mixture containing diimidedicarboxylic acids represented by theabove-mentioned formula 1, formula 2 and formula 3 are set in thefollowing manner: the mole ratio between the total number of moles ofdiamine (1′) having three or more aromatic rings, polyoxypropylenediamine (2′) and siloxane diamine (3′) and the number of moles of TMA,that is, ((1′)+(2′)+(3′))/TMA, is preferably set in a range from 1/2.05to 1/2.20, more preferably, from 1/2.10 to 1/2.15. When the mole ratiois less than 1/2.20, TMA tends to remain, causing a reduction in themolecular weight of the finally obtained resin; in contrast, when themole ratio exceeds 1/2.05, diamine tends to remain, causing a reductionin the molecular weight of the finally obtained resin.

Moreover, the mole ratio between the total number of moles ofdiimidedicarboxylic acids represented by the above-mentioned formula 1,formula 2 and formula 3, and the number of moles of aromaticdicarboxylic acid represented by the above-mentioned formula 4, that is,((1)+(2)+(3))/(4), is preferably set in a range from 1.0/0 to 1.0/1.2,more preferably, from 1.0/0 to 1.0/1.1. When the mole ratio exceeds1.0/1.2, the resulting resin tends to have a higher modulus ofelasticity.

Next, in order to allow a mixture (1)+(2)+(3)+(4) containing diimidedicarboxylic acids represented by the above-mentioned formula 1, formula2, formula 3 and aromatic dicarboxylic acid, and aromatic diisocyanaterepresented by the above-mentioned formula (5) to react with one anotherto obtain a modified polyamideimide resin, the mole ratio((1)+(2)+(3)+(4))/(5) is preferably set in a range from 1/1.50 to1/1.05, more preferably, from 1/1.30 to 1/1.10. In the case of the moleratio of less than 1/1.50, the resulting resin tends to have a reductionin the molecular weight, and in the case of the mole ratio exceeding1/1.05, the resulting resin also tends to have a reduction in themolecular weight.

The non-protic polar solvent is preferably an organic solvent which isnot capable of reacting with diamine having three or more aromaticrings, polyoxypropylene diamine, siloxane diamine and TMA, and specificexamples are: dimethyl acetamide, dimethyl formamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulforan andcyclohexanone. Since the imidizing reaction requires a high temperature,N-methyl-2-pyrrolidone having a high boiling point is preferably used.These may be used alone, or two or more kinds of these may be used incombination.

The moisture content contained in each of these non-protic polarsolvents is preferably set in a range from 0.1 to 0.2% by weight. In thecase of the moisture content exceeding 0.2% by weight, the reaction isnot allowed to sufficiently progress due to trimellitic acid generatedthrough hydration of TMA, with the result that the molecular weight ofthe resin tends to be lowered. Moreover, in the present invention, theused amount of non-protic polar solvent is preferably set in a rangefrom 10 to 80% by weight, more preferably, from 50 to 80% by weight,with respect to the total amount of diamine having three or morearomatic rings, polyoxypropylene diamine, siloxane diamine and TMA.Here, the used amount of less than 10% by weight tends to causedegradation in the solubility of TMA, failing to carry out a sufficientreaction, while the used amount exceeding 80% by weight tends to causeadverse effects as the industrial manufacturing method.

With respect to the aromatic hydrocarbon capable of azeotropicdistillation with water, examples thereof include toluene and xylene.

The weight average molecular weight of the modified polyamideimide resinof (A) component is preferably set in a range from 30,000 to 200,000,more preferably, from 40,000 to 150,000, most preferably, from 50,000 to100,000. The weight average molecular weight of less than 30,000 tendsto cause degradation in the strength and flexibility in a film state,and an increase in tackiness; in contrast, the weight average molecularweight exceeding 200,000 tends to cause degradation in the flexibilityand adhesiveness in a film state. Here, in the present invention, theweight average molecular weight is obtained based upon values that aremeasured by the gel permeation chromatography method, and converted by acalibration curve formed by using standard polystyrene.

With respect to the thermosetting resin of (B) component to be used inthe present invention, not particularly limited as long as it reactswith an amide group in the skeleton of the modified polyamideimide resinof (A) component through heat or the like, and preferable examplesthereof include epoxy resin, phenolic resin, bismaleimide triazine resinand the like. Among these, epoxy resin is preferably used from theviewpoints of good adhesiveness and easiness in handling, and from theviewpoint of non-flammable property, epoxy resin containing phosphoratoms in its molecule is more preferably used. These may be used alone,or two or more kinds of these may be used in combination.

With respect to the above-mentioned epoxy resin, specific examplesthereof include: phosphor-containing epoxy resins ZX-1548-1 (phosphorcontent: 2.0% by weight), ZX-1548-2 (phosphor content: 2.5% by weight),ZX-1548-3 (phosphor content: 3.0% by weight) and ZX-1548-4 (phosphorcontent: 4.0% by weight) (tradenames, made by Touto Kasei Co., Ltd.),and the like. These may be used alone, or two or more kinds of these maybe used in combination.

Moreover, the epoxy equivalent weight of the epoxy resin is preferablyset in a range from 200 to 500, more preferably, from 250 to 400.

The blended amount of the thermosetting resin of (B) component ispreferably set in a range from 10 to 100 parts by weight, morepreferably, from 30 to 80 parts by weight, most preferably, from 20 to50 parts by weight, with respect to 100 parts by weight of the modifiedpolyamideimide resin of (A) component. The blended amount of less than10 parts by weight tends to cause an insufficient non-flammable propertyand degradation in functions as a curing agent, and the blended amountexceeding 100 parts by weight results in a tight cross-linking structureof the resin after having been cured, causing brittleness.

With respect to the thermosetting resin of (B) component to be used inthe present invention, it is preferable to use a curing accelerator inaddition to the above-mentioned resin.

With respect to the curing accelerator, not particularly limited as longas it reacts with the phosphor-containing epoxy resin of (B) componentor accelerates the curing reaction between (A) component and (B)component, examples thereof include amines and imidazoles. These may beused alone or in combination of two or more kinds.

With respect to the above-mentioned amines, examples thereof includedicyandiamide, diaminodiphenyl methane and guanylurea. These may be usedalone or in combination of two or more kinds.

With respect to the above-mentioned imidazoles, examples thereof includealkyl-group-substituted imidazole such as 2-ethyl-4-methylimidazole andbenzoimidazole. These may be used alone or in combination of two or morekinds.

With respect to the blended amount of the above-mentioned curingaccelerator, in the case of the amines, it is preferably set in such amanner that the equivalent weight of the active hydrogen of amine isvirtually equal to the epoxy equivalent weight of thephosphor-containing epoxy resin. In the case of the imidazoles, theblended amount thereof is preferably set in a range from 0.1 to 2.0parts by weight with respect to 100 parts by weight of thephosphor-containing epoxy resin. When the blended amount is too small,uncured phosphor-containing epoxy resin remains, and tends to cause adecrease in the glass transition temperature of the cross-linking resin;in contrast, when the blended amount is too great, uncured curingaccelerator remains, and tends to cause degradation in the pot life,insulating property and the like.

With respect to the organic phosphor-based compound of (C) component tobe used in the present invention, examples thereof include:biphenyl-type phosphate compounds represented by the above-mentionedformula 7, aromatic condensed phosphate compounds represented by theabove-mentioned formula 8, trimethyl phosphate, triethyl phosphate,triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate,cresylphenyl phosphate, cresyldi-2,6-xylenyl phosphate,2-methacryloyloxy ethyl acid phosphate, diphenyl-2-methacryloyloxy ethylphosphate, and aromatic condensed phosphate compounds, such as CR-733S,CR-741, CR-747 and PX-200 (trade names, made by Daihachi ChemicalIndustry Co., Ltd.), SP-703 and SP-601 (trade names, made by ShikokuCorp.), and 35, 50, 65, 95 and 110 of “Leo Phos” Series (trade names,made by Ajinomoto Co., Inc.). These may be used alone or in combinationof two or more kinds.

In the above-mentioned formula 7 and formula 8, the benzene ring of thecompound may have a substituent such as an alkyl group having carbonatoms of 1 to 5. In the case when two or more of these substituentsexist, the two or more substituents may be the same or different fromeach other.

With respect to the alkyl group having 1 to 5 carbon atoms, examplesthereof include: a methyl group, an ethyl group, an n-propyl group, aniso-propyl group, an n-butyl group, an iso-butyl group, a sec-butylgroup, a tert-butyl group, a pentyl group, an isopentyl group and aneopentyl group.

The blended amount of the organic phosphor-based compound of theabove-mentioned (C) component is preferably set to 2 to 20 parts byweight with respect to 100 parts by weight of a modified polyamideimideresin having a micro-phase separation structure of component (A), morepreferably, 2 to 10 parts by weight, most preferably, 2 to 5 parts byweight. The blended amount of less than 2 parts by weight tends to causean insufficient non-flammable property, while the blended amountexceeding 20 parts by weight tends to cause degradation in the adhesiveproperty and soldering heat resistance.

The non-flammable heat-resistant resin composition of the presentinvention, made from the above-mentioned components, is preferably mixedin an organic solvent and prepared as a resin varnish having a solidcomponent content of 20 to 40% by weight, upon storage or uponapplication. Not particularly limited as long as an appropriatedissolving property is obtained, the above-mentioned organic solvent is,for example, selected from the group consisting of dimethylacetamide,dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone,γ-butyrolactone, sulforan, cyclohexanone, methylethyl ketone, methylisobutyl ketone, toluene and acetone.

Moreover, in addition to the above-mentioned respective components,additives, such as a coupling agent, a pigment, a leveling agent, ananti-foamer and an ion-trapping agent, may be appropriately added to thenon-flammable heat-resistant resin composition of the present invention,if necessary.

Upon forming an adhesive layer on a subject material by using thenon-flammable heat-resistant resin composition of the present invention,for example, the resin composition, as it is, may be applied thereon toform an adhesive layer. Moreover, an adhesive agent film, which has alayer of the non-flammable heat-resistant resin composition formed on asupport base member, may be prepared, and the layer of the non-flammableheat-resistant resin composition is laminated on the subject member sothat the adhesive layer may be formed. Furthermore, when the adhesivefilm is used, after the lamination process, the support base member maybe removed, or prior to the lamination process, the support base membermay be removed.

With respect to the adhesive film having the adhesive layer of thepresent invention, for example, after the non-flammable heat-resistantresin composition, dissolved in a predetermined organic solvent, hasbeen applied to a support member, the solvent may be dried by heating orhot-air blowing to form the corresponding adhesive film.

With respect to the support member, examples thereof include: resinfilms made from resins, such as polyolefins like polyethylene andpolyvinyl chloride, polyesters like polyethylene terephthalate,polycarbonates, polyimides and Teflon (registered trademark), metalfoils such as copper foil and aluminum foil, releasing paper and thelike. The thickness of the support member is preferably set in a rangefrom 10 to 150 μm. Here, the support member may be subjected to amatting process or a corona process so as to improve the adhesiveproperty, or may be subjected to a releasing treatment.

With respect to the above-mentioned organic solvent, not particularlylimited as long as an appropriate dissolving property is obtained,examples thereof include: ketones such as acetone, methylethyl ketoneand methylisobutyl ketone, acetates such as ethyl acetate, butylacetate, cerosolve acetate, propylene glycol monomethyl acetate andcarbitol acetate, cerosolves such as cerosolve and butyl cerosolve,carbitols such as carbitol and butyl carbitol, aromatic hydrocarbonssuch as toluene and xylene, dimethyl formamide, dimethyl acetamide andN-methyl-2-pyrrolidone. These may be used alone or two or more kinds ofthese may be used in combination.

The thickness of the non-flammable heat-resistant resin compositionlaminated on the support member is preferably set in a range from 5 to50 μm, more preferably, from 10 to 40 μm.

With respect to the product state of the above-mentioned adhesive film,examples thereof include: a sheet shape and a roll shape, which havebeen cut into a predetermined length, and the like. From the viewpointsof storing property, productivity and workability, a protective film isfurther laminated on the surface that is not made in contact with thesupport member of the adhesive layer, and this is preferably taken upinto a roll shape and stored.

With respect to the protective film, in the same manner as the supportmember, examples thereof include: films made from resins, such aspolyolefins like polyethylene and polyvinyl chloride, polyesters likepolyethylene terephthalate, polycarbonates, Teflon (registeredtrademark), and releasing paper. The thickness of the protective film ispreferably set in a range from 10 to 100 μm. Here, the protective filmmay be subjected to a matting process, a corona process or a releasingtreatment.

An adhesive layer made from the non-flammable heat-resistant resincomposition of the present invention is laminated on, for example, apolyimide film serving as a support member so that a polyimide film withan adhesive agent is formed; thus, it is possible to provide, forexample, a flexible circuit board-use cover-lay film and a base film.Moreover, by laminating a metal foil thereon, it is also possible toprovide a flexible circuit board-use substrate and the like.

EXAMPLES

The following description will discuss the present invention in moredetail by means of examples; however, these examples are intended to beillustrative only and are not intended to limit the scope of the presentinvention.

Synthesis Example of (A) Modified Polyimide Resin

To a separable flask (1 Liter) equipped with a water quantitativereceiver (25 ml) with a cock connected to a reflux condenser, athermometer and a stirrer were loaded BAPP(2,2-bis[4-(4-aminophenoxy)phenyl]propane) serving as diamine havingthree or more aromatic rings, Jeffermine D-2000 (trade name, made by SunTechnochmical Co., Ltd., amine equivalent weight: 1000 g/mol) serving aspolyoxypropylene diamine, reactive silicone oil X-22-161B (trade name,made by Shin-Etsu Chemical Co., Ltd., amine equivalent weight: 1540g/mol) serving as siloxane diamine, TMA (trimellitic anhydride), NMP(N-methyl-2-pyrrolidone) serving as a non-protic solvent and γ-BL(γ-butyrolactone), respectively at ratios of blend as shown in Table 1,and were stirred at 80° C. for 30 minutes. To this was further added 100ml of toluene serving as aromatic hydrocarbon capable of azeotropicdistillation with water, and this was then heated and subjected to areflux process at about 160° C. for 2 hours.

After having confirmed that about not less than 3.6 ml of water wasstored in the water quantitative receiver and that there was no waterflow, the system was heated to about 190° C. to remove toluene, whilethe released water, stored in the water quantitative receiver, was beingremoved.

Thereafter, the solution was cooled to room temperature, and to thiswere added terephthalic acid serving as aromatic dicarboxylic acid andMDI (4,4′-diphenyl methane diisocyanate) and TDI(2,4-tolylenediisocyanate), serving as aromatic diisocyanate, at addedamounts shown in Table 1, and this was allowed to react at 190° C. for 2hours. After completion of the reaction, NMP/γ-BL solutions A-1 to A-4,which were modified polyamideimide resins, were obtained. TABLE 1Blended Amounts (Parts by weight) Items A-1 A-2 A-3 A-4 BAPP 38.3 34.325.7 1.5 Jeffermine D-2000 72.6 90.0 125.0 90.0 X-22-161B 63.1 66.2 77.081.4 TMA 60.5 60.5 60.5 30.2 NMP 271.0 288.0 287.0 246.0 γ-BL 271.0288.0 287.0 246.0 Terephthalic Acid 0 0 0 14.4 MDI 27.0 27.0 27.0 27.0TDI 12.5 12.5 12.5 12.5 Nonvolatile contents 32.0 32.0 32.0 32.0 (weight%) Weight-average molecular 85000 80000 75000 75000 weight

Examples 1 to 3 and Comparative Example 1

Each of materials shown in Table 2 was blended to each of the modifiedpolyamideimide resin solutions (A-1 to A-4) obtained through theabove-mentioned synthesis example, and after this had been stirred forabout 1 hour until the resin was evenly dispersed, this was allowed tostand still at room temperature for 24 hours for defoaming to obtain aresin composition.

The resulting resin composition was applied onto a polyimide film(Capton 100H: trade name, made by Toray-Du Pont Co., Ltd.) having athickness of 25 μm so as to form a film thickness of 20 μm after thedrying process, and this was dried at 130° C. for 10 minutes, and onthis was further laminated the roughened surface side of a rolled copperfoil (BHY-22B-T: trade name, made by Nikko Glued Foil Co., Ltd.) havinga thickness of 35 μm, and this was provisionally bonded through athermal roll laminating process at a temperature of 140° C. under apressure of 0.5 MPa, and cured at 160° C. for 120 minutes by a dryer;thus, a sample was prepared (Sample A).

Moreover, the resulting resin composition was applied onto a polyimidefilm (Capton 100H: trade name, made by Toray-Du Pont Co., Ltd.) having athickness of 25 μm so as to form a film thickness of 20 μm after thedrying process, and this was dried at 130° C. for 10 minutes, and onthis was further laminated the gloss surface side of a rolled copperfoil (BHY-22B-T: brand name, made by Nikko Glued Foil Co., Ltd.) havinga thickness of 35 μm, and this was provisionally bonded through athermal roll laminating process at a temperature of 140° C. under apressure of 0.5 MPa, and cured at 160° C. for 120 minutes by a dryer;thus, a sample was prepared (Sample B).

Furthermore, the resulting resin composition was applied onto apolyimide film (Capton 100H: trade name, made by Toray-Du Pont Co.,Ltd.) having a thickness of 25 μm so as to form a film thickness of 20μm after the drying process, and this was dried at 130° C. for 10minutes, and the resulting film was cured at 160° C. for 120 minutes bya dryer; thus, a sample was prepared (Sample C).

The resulting resin composition was applied onto a Teflon (registeredtrademark) film (Nafron Tape TOMBO9001, trade name, made by Nichiasu K.K.) having a thickness of 50 μm so as to form a film thickness of 20 μmafter the drying process, and this was dried at 130° C. for 10 minutes,and the resulting film was cured at 160° C. for 120 minutes by a dryer;thus, a cured film with a Teflon (registered trademark) film wasobtained, and the Teflon (registered trademark) film was separatedtherefrom to prepare a sample (Sample D).

Further, the resulting resin composition was applied onto a polyimidefilm (Capton 100H: trade name, made by Toray-Du Pont Co., Ltd.) having athickness of 25 μm so as to form a film thickness of 25 μm after thedrying process, and this was dried at 130° C. for 10 minutes; thus, asample was prepared (Sample E).

Moreover, the resulting resin composition was applied onto a Teflon(registered trademark) film (Nafron Tape TOMBO9001, trade name, made byNichiasu K. K.) having a thickness of 50 μm so as to form a filmthickness of 25 μm after the drying process, and this was dried at 130°C. for 10 minutes, and the Teflon (registered trademark) film wasseparated from the resulting film to prepare a sample (Sample F). TABLE2 Blended Amounts (Parts by weight) Comparative Examples Example Items 12 3 4 1 (A) Modified polyamideimide resin 219 Component solution (A-1)Solid component 32% by weight Modified polyamideimide resin 219 solution(A-2) Solid component 32% by weight Modified polyamideimide resin 219solution (A-3) Solid component 32% by weight Modified polyamideimideresin 219 solution (A-4) Solid component 32% by weight (B)Phosphor-containing epoxy resin: 30 30 30 30 70 Component ZX-1548-2*¹(C) Biphenyl-type phosphate: CR-747*² 5 5 5 5 8 Component Other Dicyanamide 0.15 0.15 0.15 0.15 components 2-ethyl-4-methyl imidazole 0.2 0.20.2 0.2 0.2 Phenol novolak resin: TD2131*³ 30 Triphenyl phosphine 1*¹Trade name made by Touto Kasei Co., Ltd.*²Trade name made by Daihachi Chemical Industry Co., Ltd.*³Trade name made by Daicel Chemical Industries, Ltd.

By using these samples, measurements were carried out on the followingproperties: adhesiveness (Samples A and B), solder heat resistance(Sample A), non-flammable property (Sample C), coefficient of thermalexpansion (Sample D), glass transition temperature (Sample D), storageelastic modulus (Sample D), warping after drying (Sample E) and residualsolvent (Sample F), and the results are shown in Table 3. Measuringmethods and conditions of these characteristics are shown below:

(Adhesiveness)

Peeling tests were carried out on sample A (sample structure: polyimidefilm/resin composition/rolled copper foil roughened surface) and sampleB (sample structure: polyimide film/resin composition/rolled copper foilgloss surface) by drawing the rolled copper foil in 900 direction underthe following conditions; thus, the peel strength (kN/m) was measuredbetween the rolled copper foil roughened surface and the polyimide filmas well as between the rolled copper foil gloss surface and thepolyimide film.

Measuring temperature: 25° C., Peeling speed: 50 mm/min

(Solder Heat Resistance)

Sample A (sample structure: polyimide film/resin composition/rolledcopper foil roughened surface) was immersed into a solder bath of 300°C. for 3 minutes, and examined for any abnormal external appearancessuch as swelling and peeling.

-   ◯: There were no abnormal external appearances such as swelling and    peeling.-   X: There were abnormal external appearances such as swelling and    peeling.    (Non-Flammable Property)

Sample C (sample structure: polyimide film/resin composition) wassubjected to measurements for non-flammable property grade in compliancewith UL94 non-flammable property standard.

(Glass Transition Temperature and Storage Elastic Modulus)

Sample D (sample structure: only cured film) was subjected to dynamicviscoelasticity measurements by using an RSA-II (trade name, made byLeometric Co., Ltd.) under the following conditions. With respect to theglass transition temperature (Tg), the maximum value of tanδ peak wasused.

Measuring mode: Peeling chuck-to-chuck distance: 22.5 mm, Measuringtemperature: −50 to 300° C., Temperature rise rate: 5° C./min, Measuringfrequency: 10 Hz, Sample size: 5 mm width×20 mm length.

(Coefficient of Thermal Expansion)

Sample D (sample structure: only cured film) was subjected tomeasurements for coefficient of thermal expansion under the followingconditions. Here, the value of coefficient of thermal expansion in arange from 0° C. to <Tg was set to α₁ and the value of coefficient ofthermal expansion in a range from Tg<to 300° C. was set to α₂

-   -   Measuring device: TMA (made by Seiko Instruments Inc.)    -   Measuring modes: Peeling measurement temperature: 0 to 300° C.,        Temperature rise rate: 5° C./min.        (Warping after Drying)

Sample E (sample structure: polyimide film/resin composition) was placedon a horizontal plane, and the height of warping of the sample wasmeasured.

-   ◯: There was no warping (height: 0 mm)-   Δ: There was slight warping (height <10 mm)-   X: There was warping (height >10 mm in a curled shape)    (Residual Solvent)

Sample F (sample structure: only dried film) was cut into apredetermined area, and the weight thereof was measured (W0). This wasdried at 200° C. for one hour (W1). The residual solvent was calculatedbased upon the following equation.Residual solvent (%)=(W0−W1)/W0×100 TABLE 3 Comparative Examples ExampleItems 1 2 3 4 1 Warping after drying ◯ ◯ ◯ ◯ X Non-flammable property(UL 94) V-0 V-0 V-0 V-0 V-0 Adhesiveness Rolled copper foil 1.3 1.4 1.41.3 0.9 (KN/m) Roughened surface Rolled copper foil 1.2 1.4 1.4 1.3 0.4Gloss surface Polyimide film 1.8 1.9 1.9 1.8 0.2 Set temperature Tg 180170 160 150 130 (° C.) Tg1 (<Tg) 25 25 25 25 25 Tg2 (>Tg) 250 250 250250 250 Storage elastic E1 (<Tg) 400 250 100 600 83 modulus E2 (>Tg)0.05 0.02 0.01 50 0.001 (Mpa) Coefficient of α1 (<Tg) 0.21 0.3 4.0 0.210.0 thermal expansion α2 (>Tg) 4.0 2.5 2.0 0.13 50.0 (×10⁻³/K) Internalstress (MPa) 13.0 10.9 5.4 17.9 87.2 Solder heat resistance (300° C.) ◯◯ ◯ ◯ X Residual solvent (%) 0.5 0.5 0.5 0.6 10.5

The non-flammable heat-resistant resin composition of the presentinvention have superior properties such as a superior thermal-stressreducing effect derived from a polyoxypropylene unit and a siloxane unitof modified polyamideimide resin, a non-flammable property derived froman aromatic unit and a siloxane unit of modified polyamideimide resin, asuperior halogen-free non-flammable property derived from aphosphor-based compound serving as a non-flammable assistant agent and asuperior adhesive property derived from a stress-alleviating function ofa micro phase separation structure of modified polyamideimide resin;thus, this resin composition is effectively used as adhesives forvarious printed circuit boards, adhesive films and the like.

Moreover, the adhesive film of the present invention exerts a superiorthermal-stress reducing effect derived from a polyoxypropylene unit anda siloxane unit of modified polyamideimide resin, a non-flammable effectderived from an aromatic unit and a siloxane unit of modifiedpolyamideimide resin, a superior halogen-free non-flammable effectderived from a phosphor-based compound serving as a non-flammableassistant agent and a superior adhesive property derived from astress-alleviating function of a micro phase separation structure ofmodified polyamideimide resin.

The polyimide film with the adhesive of the present invention exerts asuperior thermal-stress reducing effect derived from a polyoxypropyleneunit and a siloxane unit of modified polyamideimide resin, anon-flammable effect derived from an aromatic unit and a siloxane unitof modified polyamideimide resin, a superior halogen-free non-flammableeffect derived from a phosphor-based compound serving as a non-flammableassistant agent and a superior adhesive property derived from astress-alleviating function of a micro phase separation structure ofmodified polyamideimide resin.

While the invention has been described in detail with reference tospecific examples thereof, it will be apparent to one skilled in the artthat various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

1. A non-flammable heat-resistant resin composition, comprising: (A)modified polyamideimide resin, (B) thermosetting resin and (C) organicphosphorus-based compound, wherein a cured film, obtained from thenon-flammable heat-resistant resin composition, exerts a storage elasticmodulus of 700 MPa or less, a coefficient of thermal expansion of5×10⁻³/K or less and an internal stress of 20 MPa or less, in atemperature range of 25 to 250° C.
 2. The non-flammable heat-resistantresin composition according to claim 1, wherein: (A) modifiedpolyamideimide resin is synthesized in the presence of a non-proticpolar solvent, and resin varnish containing the solvent is dried at 120to 140° C. for 5 to 15 minutes so that the content of the non-proticpolar solvent becomes 1% or less.
 3. The non-flammable heat-resistantresin composition according to claim 1, which contains 10 to 100 partsby weight of (B) thermosetting resin and 2 to 20 parts by weight of (C)organic phosphorus-based compound, with respect to 100 parts by weightof (A) modified polyamideimide resin.
 4. The non-flammableheat-resistant resin composition according to claim 1, wherein (A)modified polyamideimide resin is a modified polyamideimide resin that isobtained by allowing a mixture containing diimide dicarboxylic acid,represented by the following formula 1, formula 2 and formula 3 obtainedthrough a reaction between a mixture of diamine having three or morearomatic rings, polyoxypropylene diamine and siloxane diamine, andtrimellitic anhydride;

[in the formula, R¹ represents:

(where X represents

[in the formula, R² represents:

(where n represents an integer of 1 to 70).]

[in the formula, R³ represents:

(where R⁴ and R⁵ independently represent divalent organic groups, eachof R⁶ to R⁹ independently represents an alkyl group having 1 to 20carbon atoms or an aryl group having 6 to 18 carbon atoms, and mrepresents an integer of 1 to 50)] and aromatic dicarboxylic acid,represented by the following formula 4, to coexist;HOOC—R¹⁰—COOH  (Formula 4) [in the formula, R¹⁰ represents:

and by also allowing aromatic diisocyanate, represented by the followingformula 5, to react with the mixture.NCO—R¹¹—NCO  (Formula 5) [in the formula, R¹¹ represents:


5. The non-flammable heat-resistant resin composition according to claim4, wherein the polyoxypropylene diamine has an amine equivalent weightin a range from 100 to 2,000 g/mol.
 6. The non-flammable heat-resistantresin composition according to claim 4, wherein the siloxane diamine hasan amine equivalent weight in a range from 400 to 2,500 g/mol.
 7. Thenon-flammable heat-resistant resin composition according to claim 1,wherein (A) modified polyamideimide resin is synthesized in the presenceof a basic catalyst.
 8. The non-flammable heat-resistant resincomposition according to claim 7, wherein the basic catalyst is trialkylamine represented by the following formula
 6.

(in the formula, each of R¹² to R¹⁴ represents an alkyl group having 1to 8 carbon atoms.)
 9. The non-flammable heat-resistant resincomposition according to claim 1, wherein (B) thermosetting resin ismade from an epoxy resin and a curing accelerator thereof or a curingagent thereof.
 10. The non-flammable heat-resistant resin compositionaccording to claim 9, wherein the epoxy resin is a phosphorus-containingepoxy resin.
 11. The non-flammable heat-resistant resin compositionaccording to claim 1, wherein (C) organic phosphorus-based compound is aphosphate-based compound represented by the following formula 7,

(in the formula, W represents a single bond, or a bonding group, —S—,—SO₂—, —O—, or —N═N—, and n₁ is an integer of 10 to 50) or aphosphate-based compound represented by the following formula
 8.

(in the formula, n₂ is an integer of 10 to 50).
 12. An adhesive filmcomprising at least a non-flammable heat-resistant resin compositiondisclosed in claim 1 and a support member for supporting the resincomposition.
 13. The adhesive film according to claim 12, wherein thesupport member is a polyimide film.
 14. The non-flammable heat-resistantresin composition according to claim 2, which contains 10 to 100 partsby weight of (B) thermosetting resin and 2 to 20 parts by weight of (C)organic phosphorus-based compound, with respect to 100 parts by weightof (A) modified polyamideimide resin.
 15. The non-flammableheat-resistant resin composition according to claim 2, wherein (A)modified polyamideimide resin is a modified polyamideimide resin that isobtained by allowing a mixture containing diimide dicarboxylic acid,represented by the following formula 1, formula 2 and formula 3 obtainedthrough a reaction between a mixture of diamine having three or morearomatic rings, polyoxypropylene diamine and siloxane diamine, andtrimellitic anhydride;

[in the formula, R¹ represents:

(where X represents

[in the formula, R² represents:

(where n represents an integer of 1 to 70).]

[in the formula, R³ represents:

(where R⁴ and R⁵ independently represent divalent organic groups, eachof R⁶ to R⁹ independently represents an alkyl group having 1 to 20carbon atoms or an aryl group having 6 to 18 carbon atoms, and mrepresents an integer of 1 to 50)] and aromatic dicarboxylic acid,represented by the following formula 4, to coexist;HOOC—R¹⁰—COOH  (Formula 4) [in the formula, R¹⁰ represents:

and by also allowing aromatic diisocyanate, represented by the followingformula 5, to react with the mixture.NCO—R¹¹—NCO  (Formula 4) [in the formula, R¹¹ represents:


16. The non-flammable heat-resistant resin composition according toclaim 3, wherein (A) modified polyamideimide resin is a modifiedpolyamideimide resin that is obtained by allowing a mixture containingdiimide dicarboxylic acid, represented by the following formula 1,formula 2 and formula 3 obtained through a reaction between a mixture ofdiamine having three or more aromatic rings, polyoxypropylene diamineand siloxane diamine, and trimellitic anhydride;

[in the formula, R¹ represents:

(where X represents

in the formula, R² represents:

(where n represents an integer of 1 to 70).]

[in the formula, R³ represents:

(where R⁴ and R⁵ independently represent divalent organic groups, eachof R⁶ to R⁹ independently represents an alkyl group having 1 to 20carbon atoms or an aryl group having 6 to 18 carbon atoms, and mrepresents an integer of 1 to 50)] and aromatic dicarboxylic acid,represented by the following formula 4, to coexist;HOOC—R¹⁰—COOH  (Formula 4) [in the formula, R¹⁰ represents:

and by also allowing aromatic diisocyanate, represented by the followingformula 5, to react with the mixture.NCO—R¹¹—NCO  (Formula 5) [in the formula, R¹¹ represents:


17. The non-flammable heat-resistant resin composition according toclaim 2, wherein (A) modified polyamideimide resin is synthesized in thepresence of a basic catalyst.
 18. The non-flammable heat-resistant resincomposition according to claim 3, wherein (A) modified polyamideimideresin is synthesized in the presence of a basic catalyst.
 19. Thenon-flammable heat-resistant resin composition according to claim 2,wherein (B) thermosetting resin is made from an epoxy resin and a curingaccelerator thereof or a curing agent thereof.
 20. The non-flammableheat-resistant resin composition according to claim 3, wherein (B)thermosetting resin is made from an epoxy resin and a curing acceleratorthereof or a curing agent thereof.
 21. The non-flammable heat-resistantresin composition according to claim 2, wherein (C) organicphosphorus-based compound is a phosphate-based compound represented bythe following formula 7,

(in the formula, W represents a single bond, or a bonding group, —S—,—SO₂—, —O—, or —N═N—, and n₁ is an integer of 10 to 50) or aphosphate-based compound represented by the following formula
 8.

(in the formula, n₂ is an integer of 10 to 50).
 22. The non-flammableheat-resistant resin composition according to claim 21, wherein saidbonding group represented by W in Formula 7 is an alkylene group having1 to 5 carbon atoms.
 23. The non-flammable heat-resistant resincomposition according to claim 3, wherein (C) organic phosphorus-basedcompound is a phosphate-based compound represented by the followingformula 7,

(in the formula, W represents a single bond, or a bonding group, —S—,—SO₂—, —O—, or —N═N—, and n₁ is an integer of 10 to 50) or aphosphate-based compound represented by the following formula
 8.

(in the formula, n₂ is an integer of 10 to 50).
 24. The non-flammableheat-resistant resin composition according to claim 21, wherein saidbonding group represented by W in Formula 7 is an alkylene group having1 to 5 carbon atoms.
 25. An adhesive film comprising at least anon-flammable heat-resistant resin composition disclosed in claim 2 anda support member for supporting the resin composition.
 26. An adhesivefilm comprising at least a non-flammable heat-resistant resincomposition disclosed in claim 3 and a support member for supporting theresin composition.
 27. The non-flammable heat-resistant resincomposition according to claim 11, wherein said bonding grouprepresented by W in Formula 7 is an alkylene group having 1 to 5 carbonatoms.